JPH05201980A - Methoxyiminoacetic acid derivative and agricultural and horticultural fungicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To provide a new compound, harmless to plants, also low toxic to man and livestock and fish, having excellent controlling activity on the pathogenic bacteria for a variety of plants, thus useful for agricultural/horticultural bactericides, etc. CONSTITUTION:The objective compound of formula I [Y is of formula II (R<1> and R<2> are each H or 1-5C alkyl), etc.; Z is (substituted) 1-6C alkyl, (substituted) 3-6C cycloalkyl, (substituted) 2-6C alkenyl, etc.; A is methoxy or methylamino; m is 0 or 1], e.g. methyl-2-(4-benzyloxy-1,3-dimethylpyrazol-5-yl)-2- methoxyiminoacetate. The compound of the formula I can be obtained, for example, by reaction of a compound of formula IV with a compound of formula V in a solvent like THF in the presence of a base such as triethylamine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel methoxyiminoacetic acid derivative and an agricultural and horticultural fungicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
It is known that certain methoxyiminoacetic acid derivatives have biological activity such as bactericidal effect. For example, JP-A-63
-23852 discloses the following formula

[0003]

[Chemical 5]

Compounds of the formula have been described. However, as is clear from the test examples described below, these compounds have not always been sufficient as agricultural and horticultural fungicides under the present circumstances.

[0005]

Means for Solving the Problems The present inventors focused their attention on such a methoxyiminoacetic acid derivative, and as a result of extensive studies, a methoxyiminoacetic acid derivative having a specific structure has excellent bactericidal activity, Moreover, they have found that they have extremely excellent permeability to plants, and have completed the present invention.

That is, the gist of the present invention is the following general formula (I)

[0007]

[Chemical 6]

[In the above general formula (I), Y is

[0009]

[Chemical 7]

(R ¹ and R ² each independently represent a hydrogen atom or a C ₁ -C ₅ alkyl group) or

[0011]

[Chemical 8]

(R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a C ₁ -C ₃ alkyl group or a halogen atom),

[0013]

[Chemical 9]

Is a C ₁ -C ₆ alkyl group which may have a substituent, a C ₃ -C ₆ cycloalkyl group which may have a substituent, or a substituent C _{2 to} C ₆
Alkenyl group, optionally substituted C ₂ -C ₆
Alkynyl group, optionally substituted C ₁ -C ₆
Alkoxy group, halogen atom, nitro group, cyano group,
It has one or more substituents selected from a C _{6 to} C ₁₂ aryloxy group which may have a substituent and a heteroaryloxy group which has a total number of atoms of 5 to 14 which may have a substituent. Optionally represents a phenyl group, A represents a methoxy group or a methylamino group, and m represents 0 or 1. ]
A methoxyiminoacetic acid derivative represented by and an agricultural and horticultural fungicide containing the same as an active ingredient.

The present invention will be described in detail below. The methoxyiminoacetic acid derivative of the present invention is represented by the above general formula (I). In the general formula (I), Y is

[0016]

[Chemical 10]

(R ¹ And R ² Are each independently a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, is
It represents a C ₁ -C ₅ alkyl group such as an o-propyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. R ¹ Is
It is preferably a C ₁ -C ₄ alkyl group, particularly preferably a methyl group. R ² Is preferably a C ₁ -C ₃ alkyl group, particularly preferably a methyl group. ) Or

[0018]

[Chemical 11]

(R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom; a C ₁ -C ₃ alkyl group such as a methyl group, an ethyl group or an iso-propyl group; or a halogen such as fluorine, chlorine or bromine. Represents an atom, preferably a hydrogen atom).

[0020]

[Chemical formula 12]

Is a methyl group, an ethyl group, an n-propyl group,
iso-propyl group, n-butyl group, t-butyl group, n
C such as -pentyl group and n-hexyl group₁~ C₆The archi
Group; cyclopropyl group, cyclobutyl group, cyclopen
C such as chill group and cyclohexyl group₃~ C₆The cycloal
Kill group; vinyl group, allyl group, 1-propenyl group, 3-
Butenyl group, 2-butenyl group, 1-butenyl group, 2-pentenyl group
C, such as montenyl group and 2-hexenyl group₂~ C₆Arche
Nyl group; ethynyl group, propargyl group, 2-butynyl group
Group, 2-pentynyl group, 2-hexynyl group and the like C₂~ C
₆Alkynyl group; methoxy group, ethoxy group, n-pro group
Poxy group, iso-propoxy group, n-butoxy group, t
-Butoxy group, n-pentyloxy group, n-hexyl group
C such as xy group ₁~ C₆Alkoxy group; fluorine atom, salt
Halogen atom such as elementary atom and bromine atom; Nitro group; Cyano
Group; C such as phenoxy group and naphthyloxy group₆~ C₁₂of
Aryloxy group; pyridyloxy group, thienyloxy
Group, furyloxy group, pyrrolyloxy group, imidazolyl
Oxy group, pyrazolyloxy group, pyrimidinyloxy
Group, indolyloxy group, quinolyloxy group, oxazo
Total number of atoms such as ryloxy group and thiazolyloxy group is 5 to 1
One or more substitutions selected from heteroaryloxy groups of 4
Represents a phenyl group which may have a group.

The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group and heteroaryloxy group which may be substituted on the phenyl group are each a C ₁ -C ₃ alkyl group. A group; a C _{1 to} C ₃ alkoxy group; a C _{6 to} C ₁₂ aryloxy group; a halogen atom such as a fluorine atom and a chlorine atom; a nitro group; one or more substituents selected from a cyano group and a trifluoromethyl group It may be substituted.

[0023]

[Chemical 13]

Preferably represents a phenyl group having a substituent selected from methyl, a halogen atom, a trifluoromethyl group, and a phenoxy group. The number of substituents is 1
It is preferable that it is -3. A represents a methoxy group or a methylamino group.

M represents 0 or 1. The above general formula (I)
Specific examples of the compound of the present invention represented by
1 and Table-2, the compound of the present invention is not limited to these.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Table 8]

The compound of the present invention is a novel compound and is produced, for example, according to the following reaction formula.

[0035]

[Chemical 14]

The compound represented by the general formula (Ia) is obtained by reacting the ketoester derivative represented by the general formula (II) with methoxyamine hydrochloride in the presence of a solvent inert to the reaction. Is synthesized by. In the reaction, the reaction may be carried out in the presence of a base such as potassium carbonate, sodium acetate or triethylamine. The amount of methoxyamine hydrochloride used in the reaction is usually in the range of 0.9 to 5.0 equivalents based on the ketoester derivative represented by the general formula (II). The amount of the base optionally used is usually in the range of 0.5 to 5.0 equivalents relative to the ketoester derivative represented by the general formula (II).

Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene and toluene; esters such as ethyl acetate; carboxylic acids such as acetic acid and formic acid; alcohols such as methanol and ethanol; tetrahydrofuran, dioxane and the like. Ethers; or polar solvents such as dimethyl sulfoxide, dimethylformamide, and water.

The reaction temperature is selected from the range of 0 ° C. to the boiling point of the solvent used, preferably 10 to 100 ° C.
Is. The compound represented by the general formula (Ib) is obtained by reacting the compound represented by the general formula (Ia) with methylamine. The amount of methylamine used is in the range of 1 equivalent to a large excess with respect to the ester derivative of the general formula (Ia). Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; and polar solvents such as dimethyl sulfoxide, dimethylformamide and water. Can be mentioned.

The reaction temperature is selected from the range of 0 ° C. to the boiling point of the solvent used, preferably 10 ° to 80 ° C.
Is. The keto ester derivative represented by the general formula (II) as a starting material is produced by the method described in US Pat. No. 5,055,477 or JP-A-63-23852, or a method analogous thereto.

The compounds of the present invention thus obtained are all novel and have excellent bactericidal activity. In particular, since it has an excellent control effect against disease fungi of various plants, it is useful as an agricultural and horticultural fungicide. For example, rice blast ( Phricularia oryzae ); rice blight ( Rhizoctonia solani );
Various rust diseases of wheat ( Puccinia recondi
ta ); powdery mildew of various crops ( Erysiphe g
raminis ); Gray mold of vegetables and fruit trees ( Bo
trytis cinerea ); Eki disease of various crops ( Phytophthora infestance )
It is useful as an agricultural and horticultural fungicide because it not only has high activity against the like, but also has extremely excellent permeability to plants.

The compounds of the present invention are also extremely useful for controlling plant diseases because they have low toxicity to humans and animals. In using the compound of the present invention as an agricultural and horticultural fungicide, this compound may be used as it is, but in order to make effective dispersion of the active ingredient in the application scene, an auxiliary agent is added according to a conventional method, and the emulsion is prepared. It is preferably used in the form of a wettable powder, a powder or the like.

Examples of the solvent, which is one of the auxiliary agents in the agricultural and horticultural germicide of the present invention, include water, alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.). ), Ethers (ethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (kerosene, kerosene, fuel oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), Halogenated hydrocarbons (dichloroethane, trichlorobenzene, carbon tetrachloride, etc.), acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, glycerin ester of fatty acids, etc.), nitriles (acetonitrile, etc.), etc. Suitable, one or more of these Mixture is used.

As the extender, clay such as kaolin and bentonite, talc such as talc and pyrophyllite, diatomaceous earth, mineral powder such as oxide such as white carbon and soybean powder, carboxymethylcellulose (CMC) Plant powders such as and the like are suitable, and one kind or a mixture of two or more kinds thereof is used. Moreover, you may use surfactant as a spreading agent, a dispersing agent, an emulsifier, and a penetrating agent. Examples of the surfactant include nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.), cationic surfactants (alkyldimethylbenzylammonium chloride, alkylpyridinium chloride, etc.), Anionic surfactants (alkylbenzene sulfonate, lignin sulfonate, higher alcohol sulfate), amphoteric surfactants (alkyl dimethyl betaine, dodecylaminoethylglycine, etc.) and the like can be mentioned. These surfactants are used as one kind or as a mixture of two or more kinds depending on the application.

When the agricultural or horticultural fungicide of the present invention is applied in the form of emulsion, the compounds of the present invention 10 to 10 are used.
80 parts, preferably 10-70 parts, solvent 10-90 parts,
A mixture of 20 to 80 parts and 3 to 20 parts, preferably 5 to 15 parts of a surfactant in an appropriate ratio is used as a raw material, which is diluted with water to a predetermined concentration at the time of use and then dispersed by a method such as spraying. Apply.

When used in the form of a wettable powder, 5 to 80 parts, preferably 10 to 70 parts, and 10 to 90 parts, preferably 20 to 80 parts, of the compound of the present invention and surfactant 1 are used.
.About.20 parts, preferably 3 to 15 parts are mixed in an appropriate ratio and the mixture is diluted with water or the like as in the case of the emulsion and used. When used in the form of powder, the compound of the present invention is usually added in an amount of 0.1 to 10 parts, preferably 1 to 5 parts by weight, such as kaolin, bentonite, talc and the like 90 to 99.9 parts, preferably 95 to 99. Use evenly mixed with the parts.

The agricultural / horticultural fungicide of the present invention may be used in admixture with other active ingredients which do not inhibit the fungicidal effect of the present active ingredient, such as fungicides, insecticides and acaricides. You can also The fungicide for agricultural and horticultural use of the present invention can be suitably applied to both foliar application and water surface application. In the case of foliar application, it is usually diluted with water so as to contain 10 to 1000 ppm of emulsion or wettable powder, and 10 to 500 per 10 are.
Apply liters.

[0047]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the following description, "part" means "part by weight". Further, the compounds of the present invention synthesized in Production Examples are shown in Table 3 and Table 4,
The production of each of these was confirmed by elemental analysis, IR spectrum, NMR spectrum and the like.

Example 1 Synthesis of methyl 2- (4-benzyloxy-1,3-dimethylpyrazol-5-yl) -2-methoxyiminoacetate (Synthesis of compounds No. 1 and 2 in Table 3) Methyl 2- (4-benzyloxy-1,3-dimethylpyrazol-5-yl) -2-oxoacetate (1
A mixture of 0.0 g, 0.0347 mol), O-methylhydroxyamine (3.48 g, 0.0416 mol), sodium acetate (14.2 g, 0.175 mol) and methanol (50 ml) was refluxed for 6 hours. After completion of the reaction, the solvent was distilled off, the reaction mixture was poured into water (30 ml) and extracted with ethyl acetate (100 ml), the organic layer was washed with water (20 ml) and dried over magnesium sulfate, and then the solvent was distilled off. The residue is separated and purified by silica gel column chromatography (eluent: 20-60% / ethyl acetate /
n-hexane) to give the desired product (Z-form, 1.0
0 g, 9%) and (E form, 1.50 g, 14%) were obtained.

Table 3 is exactly the same except that the raw materials were changed.
Compound No. 5,7,8,9,10 and 13 were synthesized.

Example 2 Synthesis of N-methyl 2- (4-benzyloxy-1,3-dimethylpyrazol-5-yl) -2-methoxyiminoacetamide (synthesis of compound No. 3 in Table 3) Methyl 2- (4-benzyloxy-1,3-dimethylpyrazol-5-yl) -2-methoxyiminoacetate (0.5 g, E form) in methylamine-water solution (3 m
l) was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the solvent was distilled off, and the residue was separated and purified by silica gel column chromatography (eluent: 20-60% / ethyl acetate / n-hexane) to give the desired product (E-form, 0.
5 g, quant. ) Got

Compound No. 3 in Table 3 was similarly prepared except that the raw materials were changed. 4, 6, 11, 12 and 14 were synthesized.

Example 3 Methyl 2- (2-phenoxypyridin-3-yl)-
Synthesis of 2-methoxyiminoacetate (Synthesis of Compound Nos. 1 and 2 in Table 4) Methyl 2- (2-phenoxypyridin-3-yl)-
2-oxoacetate (5.00 g, 19.5 mmo
l) and O-methylhydroxyamine (8.12 g, 9
7.5 mmol) and sodium acetate (12.8 g, 0.
A mixture of 156 mol) and methanol (50 ml),
Refluxed for 6 hours. After completion of the reaction, the solvent was distilled off and the water (3
Pour the reaction mixture into 0 ml) and wash with ethyl acetate (100 m).
l) Extraction, the organic layer was washed with water (20 ml) and dried over magnesium sulfate, and then the solvent was distilled off. The residue is separated and purified by silica gel column chromatography (eluent: 5-
40% / ethyl acetate / n-hexane)
Target product (Z form, 1.40 g, 25%) and (E form,
2.91G, 52%) was obtained.

Compound No. 1 in Table 4 was similarly prepared except that the raw materials were changed. 5, 7 and 9 were synthesized.

Example 4 Synthesis of N-methyl 2- (2-phenoxypyridin-3-yl) -2-methoxyiminoacetamide (Synthesis of compound No. 3 in Table 4) Methyl 2- (2-phenoxy) Pyridin-3-yl)-
Methylamine-aqueous solution (3 ml) was added to 2-methoxyiminoacetate (0.5 g, E-form), and the mixture was stirred at room temperature overnight. After completion of the reaction, the solvent was distilled off, and the residue was separated and purified by silica gel column chromatography (eluent:
20-60% / ethyl acetate / n-hexane) to obtain the desired product (E form, 0.5 g, quant.).

Compound No. 1 in Table 4 was similarly prepared except that the raw materials were changed. 4, 6, 8 and 10 were synthesized.

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

Formulation Example 1 No. 1 part of compound 20 parts, diatomaceous earth 75
Parts, and 5 parts of a surfactant containing alkylbenzene sulfonic acid as a main component were uniformly pulverized and mixed to obtain a wettable powder.

Formulation Example 2 No. 40 parts of 10 compounds, 10 parts of white carbon, 47 parts of diatomaceous earth, "Sorbol" 5039
A wettable powder was obtained by uniformly pulverizing and mixing 3 parts (a trademark of Toho Chemical Industry Co., Ltd., a surfactant containing polyoxyethylene alkylaryl ether sulfonate as a main component).

Formulation Example 3 No. 30 parts of the compound of No. 5 and "Sorbol" 3005X (trademark of Toho Chemical Industry Co., Ltd., a mixture of a nonionic surfactant and an anionic surfactant) 15
Parts, xylene 25 parts, and dimethylformamide 30 parts were mixed and dissolved to obtain an emulsion.

Formulation Example 4 No. 2 parts of the compound of 1 and 98 parts of N, N-kaolin clay (manufactured by Tsuchiya Kaolin Co., Ltd.) were mixed and pulverized to obtain a powder.

Next, the usefulness of the compound of the present invention as an agricultural and horticultural fungicide will be clarified by giving test examples. In addition, as a comparative control, compound No. The compound of A was used.

[0068]

[Table 16]

Test Example 1 Wheat Powdery Mildew Control Effect Test A wettable powder prepared in the same manner as in Formulation Example 1 with water was applied to wheat (cultivar: Norin 61) at the 1-2 leaf stage which was raised in a pot having a diameter of 6 cm. 10 ml per pot after diluting to the specified concentration
The foliage was sprayed at the ratio of. After air-drying the chemical solution, wheat powdery mildew (Erysiphe graminis ( Erysiphe gra
After spray-inoculating with a spore suspension obtained from a wheat leaf that had been infected with ( minis ), it was allowed to stand in a greenhouse for 7 to 10 days.

For the evaluation, the diseased area ratio of each leaf was evaluated and the control value was calculated by the following formula. The results are shown in Table-6.

[Table 17]

[0071]

[Table 18]

[0072]

The compounds of the present invention thus obtained are all novel compounds and have excellent bactericidal activity. In particular, since it has an excellent control effect against disease fungi of various plants, it is useful as an agricultural and horticultural fungicide. For example, rice blast ( Phricularia oryza)
e ); Rice blight ( Rhizoctinia sola)
ni ); Various rust diseases of wheat ( Puccinia rec)
ondita ); powdery mildew of various crops ( Erysip
he graminis ); Botrytis cinerea of vegetables, fruit trees, etc .; Phytophthora infestan of various crops
ce ) and the like, as well as having extremely high permeability to plants, they are useful as agricultural and horticultural fungicides.

Further, since the compound of the present invention has almost no harmful effect on plants and has low toxicity to human livestock or fish, it is extremely useful for controlling plant diseases.

Claims (2)

[Claims] 1. The following general formula (I): [In the above general formula (I), Y is (R ¹ and R ² are each independently a hydrogen atom or C
It represents an alkyl group having ₁ -C _5. ) Or [Chemical 3] (R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom,
It represents an alkyl group or a halogen atom C ₁ -C _3. )
And represents Is a C ₁ -C ₆ alkyl group which may have a substituent,
A C ₃ -C ₆ cycloalkyl group which may have a substituent, a C ₂ -C ₆ alkenyl group which may have a substituent, and a C ₂ -C which may have a substituent ₆ alkynyl group, optionally substituted C _{1 to} C ₆ alkoxy group, halogen atom, nitro group, cyano group, optionally substituted C _{6 to} C ₁₂ aryloxy group And a phenyl group which may have one or more substituents selected from a heteroaryloxy group having 5 to 14 total atoms which may have a substituent, and A represents a methoxy group or a methylamino group. And m represents 0 or 1. ] The methoxyimino acetic acid derivative represented by these. 2. An agricultural and horticultural fungicide containing the methoxyiminoacetic acid derivative according to claim 1 as an active ingredient.